EP0885911B1 - Two-component catalyst for ring-opening metathesis polymerization - Google Patents

Two-component catalyst for ring-opening metathesis polymerization Download PDF

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Publication number
EP0885911B1
EP0885911B1 EP98810442A EP98810442A EP0885911B1 EP 0885911 B1 EP0885911 B1 EP 0885911B1 EP 98810442 A EP98810442 A EP 98810442A EP 98810442 A EP98810442 A EP 98810442A EP 0885911 B1 EP0885911 B1 EP 0885911B1
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European Patent Office
Prior art keywords
component
compound
formula
catalyst system
phosphite
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EP98810442A
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German (de)
French (fr)
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EP0885911A1 (en
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Andreas Hafner
Paul Adriaan Van Der Schaaf
Andreas MÜHLEBACH
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BASF Schweiz AG
Ciba SC Holding AG
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Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium

Definitions

  • the present invention relates to a 2-component catalyst system for the ring-opening Metathesis Polymerization (ROMP), a curable system containing one Catalyst system, a process for the production of moldings and the use of the curable system as a wrapping material for electrical or electronic components.
  • ROMP ring-opening Metathesis Polymerization
  • the object of the present invention was to be stable against air and moisture 2-component catalyst system for ring-opening metathesis polymerization with to provide sufficient reactivity for the RIM process.
  • the ruthenium compounds of the formulas I or II can be prepared by known methods Implementation of ruthenium dihalides with the corresponding arenes, nitriles, amines, Phosphines or phosphites are produced.
  • Suitable C 1 -C 18 alkyl cyanides as ligands L 1 to L 4 are, for example, acetonitrile, propionitrile, n-butyronitrile, isobutyronitrile, pivalonitrile, neo-pentyl cyanide, valeronitrile, capronitrile, n-heptyl cyanide, n-octyl cyanide and n-nonyl cyanide -Decylcyanid.
  • suitable C 6 -C 24 aralkyl cyanides are phenylacetonitrile, 3-phenylpropionitrile, 4-phenylbutyronitrile and naphthylacetonitrile.
  • Tertiary amines as ligands L 1 to L 4 are, for example, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-tert.-butylamine, benzyldimethylamine, triphenylamine, tricyclohexylamine, phenyldimethylamine, cyclyldietylamine amine, phenyldietylamine amine , Urotropin, triethylenediamine, N-methylpiperidine and N-ethylpiperidine.
  • L 1 to L 4 as tertiary phosphine can be, for example, trimethylphosphine, triethylphosphine, trin-propylphosphine, tri-n-butylphosphine, triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tri-n-octylphosphine, tritolylphosphine or a compound of the formula III wherein R is C 1 -C 18 alkyl, C 5 -C 14 aryl or C 6 -C 24 aralkyl.
  • the alkyl groups can be straight-chain or branched and preferably contain 1 to 12, particularly preferably 1 to 8 and particularly preferably 1 to 4 carbon atoms.
  • Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups.
  • R as aryl preferably contains 6 to 10 carbon atoms. It can be, for example, phenyl, tolyl, pentalinyl, indenyl, naphthyl, azulinyl and anthryl.
  • R as aralkyl preferably contains 7 to 12 carbon atoms and particularly preferably 7 to 10 carbon atoms. For example, it can be benzyl, phenethyl, 3-phenylpropyl, ⁇ -methylbenzyl, 4-phenylbutyl and ⁇ , ⁇ -dimethylbenzyl.
  • Suitable phosphites as ligands L 1 to L 4 are, for example, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triphenyl phosphite, methyldiphenyl phosphite, dimethylphenyl phosphite, tri-n-octyl phosphite, tritolyl phosphite or tritolyl phosphite or tritolyl phosphite or tritolyl phosphite or tritolyl phosphite or tritolyl phosphite or compounds of formula III given above.
  • X in the formulas I or II represents fluorine, chlorine, bromine or iodine, in particular chlorine.
  • A generally stands for aromatic compounds.
  • A preferably represents unsubstituted or substituted with OH, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 6 -C 12 aryl or halogen monocyclic, polycyclic or condensed arenes with 6 to 24, preferably 6 to 18 and particularly preferably 6 to 12 carbon atoms.
  • Some examples of arenes and heteroarenes are benzene, toluene, o-xylene, p-xylene, mesitylene, Ethylbenzene, cumene, 1,3,5-triisopropylbenzene, p-cymene, durol, hexamethylbenzene, Naphthalene, biphenyl, diphenylmethane, anthracene, acenaphthene, fluorene, phenanthrene, Pyrene, chrysene, fluoranthrene, furan, thiophene, pyrrole, pyridine, ⁇ -pyran, ⁇ -thiopyran, Pyrimidine, pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran, benzthiophene, Dibenzothiophene, pyrazole, imidazole, benzimidazole, o
  • tertiary phosphines which have at least one secondary alkyl or cycloalkyl group bonded directly to the phosphorus atom are suitable as component (b) of the catalyst system according to the invention.
  • phosphines are isopropyldimethylphosphine, diisopropylmethylphosphine, isopropyldiethylphosphine, diisopropylethylphosphine, isopropyldiphenylphosphine, diisopropylphenylphosphine, tri-secylhexylphosphine, tris (1-methylbutyl) phosphine
  • component (a) is a compound of the formula II, in which A is benzene, toluene, o-xylene, p-xylene, mesitylene, ethylbenzene, cumene, 1,3,5-triisopropylbenzene, p-cymene, durol, hexamethylbenzene, naphthalene, biphenyl or Diphenylmethane stands.
  • component (a) is a compound of the formula I or II, in which one or more ligands L 1 to L 4 are acetonitrile, propionitrile, n-butyronitrile, valeronitrile or capronitrile.
  • Preferred as component (a) are also compounds of the formula I or II, in which one or more ligands L 1 to L 4 triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tri (n-butyl) phosphine, tri (n-octyl) phosphine, trimethylphosphite, triisopropylphosphite , Triphenyl phosphite, tris (p-nonylphenyl) phosphite or a compound of formula III wherein R is C 1 -C 18 alkyl, C 5 -C 14 aryl or C 6 -C 24 aralkyl.
  • a particularly preferred component (a) is a compound of the formula II in which A is p-cymene, r is 2 and L 1 is butyronitrile or capronitrile.
  • component (a) is a compound of the formula II in which A is p-cymene, r is 1, s is 0 and L 1 is triphenyl phosphite, tris (p-nonylphenyl) phosphite or 2,4,8,10 -Tetrakis (1,1-dimethylethyl) -6-methoxy-dibenzo [d, f] [1,3,2] dioxaphosphepine.
  • Triisopropylphosphine or tricyclohexylphosphine is preferably used as component (b) used.
  • Both components (a) and (b) are not reactive towards strained cycloolefins, i.e. Mixtures containing a cycloolefin and component (a) or a cycloolefin and Component (b) are stable in storage at room temperature for several months. Not until Mixing the two components creates a product that acts as a catalyst for the ring-opening metathesis polymerization works.
  • the two-component system according to the invention is therefore particularly suitable for the RIM process, since the polymerisable Cycloolefin can be divided into two portions prior to processing, using the appropriate amounts of components (a) and (b) are added. When mixing the mixture is polymerized by the two portions and injection into the preheated mold then very quickly and forms hardened products with good mechanical properties.
  • strained cycloolefins are Cycloolefins with the exception of cyclohexene and its derivatives, which are not compatible with the ring-opening metathesis can be polymerized to understand.
  • the strained cycloolefins can be monocyclic or polycyclic act as condensed or bridged ring systems, for example with two to four rings, which are unsubstituted or substituted and one or more heteroatoms, such as O, S, N or Si, in one or more rings and / or condensed aromatic or heteroaromatic rings, such as, for example, o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene, can contain.
  • the individual cyclic rings can be 3 to 16, preferably Contain 3 to 12 and particularly preferably 3 to 8 ring members.
  • the tense Cycloolefins can contain other non-aromatic double bonds, depending on Ring size preferably 2 to 4 such additional double bonds.
  • the selected monomer and the amount of catalyst also form crosslinked polymers.
  • Preferred cycloolefins are Diels-Alder adducts of cyclopentadiene.
  • Suitable Diels-Alder adducts of cyclopentadiene are, for example, the following compounds:
  • Preferred Diels-Alder adducts are norbornene (1), norbomadiene (6), Cyclohexenylnorbornene (25), Tetracyclododecen (14), Methyltetracyclododecen (11) and especially dicyclopentadiene (18).
  • thermoplastic materials can be adjusted.
  • suitable thermoplastics are polystyrene, polynorbornene (e.g. Norsorex® NS from Nippon Zeon), hydrogenated Polynorborn derivatives (e.g. Zeonex® from Nippon Zeon), polycyclooctene (e.g. Vestenamer® from Hüls) and polybutadiene.
  • the curable mixtures can contain tougheners, such as, for example, core / shell polymers or the elastomers or graft polymers containing those known to the person skilled in the art as "rubber tougers". Suitable tougheners are described, for example, in EP-A-449 776.
  • silanes e.g. from Osi Specialties under the Description Silquest® Silane offered compounds can be added.
  • suitable Silanes are, for example, octyltriethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, Methyltrimethoxysilane, vinyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane.
  • compositions according to the invention can contain other common additives, e.g. Antioxidants, light stabilizers, Plasticizers, dyes, fillers, pigments, thixotropic agents, defoamers, antistatic agents, Lubricants and mold release agents.
  • additives e.g. Antioxidants, light stabilizers, Plasticizers, dyes, fillers, pigments, thixotropic agents, defoamers, antistatic agents, Lubricants and mold release agents.
  • component (b) may contain a small amount an alkyne such as 1-heptin, 1-octyne, 1-decyne or phenylethine become.
  • a further subject of the invention is a method for producing a Metathesis polymer, characterized in that containing a composition components (c) and (d) are heated to a temperature> 40 ° C.
  • the method according to the invention is expedient at a temperature of at least 60 ° C carried out.
  • the inventive method at temperatures from 60 to 300 ° C, particularly preferably at 60 to 200 ° C and particularly preferred at 70 to 160 ° C performed.
  • Post-temper mixture at elevated temperatures, for example 80 to 200 ° C.
  • the metathesis polymers prepared by the process according to the invention can Homopolymers, copolymers with statistical distribution of the structural units, Graft polymers, block polymers or cross-linked polymers.
  • the polymers can be a average molecular weight of 500 to 2,000,000 daltons, preferably 1000 to Have 1,000,000 daltons (determined by gel permeation chromatography).
  • the polymers prepared by the process according to the invention stand out all thanks to high thermal stability, high toughness and mechanical strength as well due to excellent electrical properties (low dielectric constant, lower Loss factor or tan ⁇ value) and are suitable for applications in vacuum casting technology, as casting resins, impregnating resins and in particular as coating material for electrical and electronic components.
  • Another object of the invention is a process for the production of moldings, characterized in that a curable 2-component system containing the above specified components (c) and (d) introduced into a mold by the RIM method and is hardened.
  • curable 2-component system containing the above specified components (c) and (d) as wrapping material for electrical or Electronic components represent a further subject of the invention.
  • the dicyclopentadiene used in the examples below is degassed for about 15 minutes at room temperature under vacuum (3 mbar) and then stored under nitrogen.
  • [(p-Cymol) RuCl 2 ⁇ 2,4,8,10-tetrakis (1,1-dimethylethyl) -6-methoxy-dibenzo [d, f] [1,3,2] dioxaphosphepine ⁇ ] [(p -Cymol) RuCl 2 (triphenylphosphite)] and [(p-cymene) RuCl 2 ⁇ tris (pnonylphenyl) phosphite ⁇ ] are prepared by adding one equivalent of the corresponding phosphite to a solution of [(p-cymene) RuCl 2 ] 2 in methylene chloride. The pure products are isolated by distilling off the solvent and then washing with hexane in almost quantitative yield.

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Description

Die vorliegende Erfindung betrifft ein 2-Komponenten-Katalysatorsystem für die ringöffnende Metathesepolymerisation (ROMP), ein härtbares System enthaltend ein solches Katalysatorsystem, ein Verfahren zur Herstellung von Formkörpern sowie die Verwendung des härtbaren Systems als Umhüllungsmaterial für elektrische oder elektronische Bauteile.The present invention relates to a 2-component catalyst system for the ring-opening Metathesis Polymerization (ROMP), a curable system containing one Catalyst system, a process for the production of moldings and the use of the curable system as a wrapping material for electrical or electronic components.

Im US-Patent 4,426,502 und in der EP-A-348 852 wird die ringöffnende Metathese-Polymerisation (ROMP) von gespannten Cycloolefinen mittels des RIM-Prozesses (reaction injection molding) beschrieben. Dabei wird ein Zwei-Komponenten-System aus einem Katalysator und einem Cokatalysator für die ringöffnende Metathese-Polymerisation verwendet. Das polymerisierbare Cycloolefin wird nach dem dort beschriebenen Verfahren in zwei Portionen geteilt, wobei die eine Hälfte den Katalysator und die andere Hälfte den entsprechenden Cokatalysator enthält. Beim Vermischen der beiden Portionen und Einspritzen in die vorgewärmte Form härtet das Gemisch dann schnell aus. Die Verwendung von Organoaluminium-Verbindungen als Co-Katalysatoren erfordert allerdings den Ausschluss von Feuchtigkeit.In US Patent 4,426,502 and in EP-A-348 852 the ring opening metathesis polymerization is described (ROMP) of strained cycloolefins using the RIM process (reaction injection molding). A two-component system becomes one Catalyst and a cocatalyst for ring-opening metathesis polymerization used. The polymerizable cycloolefin is described in divided into two portions, one half the catalyst and the other half the contains the corresponding cocatalyst. When mixing the two portions and Injecting the mixture into the preheated mold quickly hardens. The usage of organoaluminum compounds as co-catalysts, however, requires that Exclusion of moisture.

In der WO 96/16100 und der WO 96/20235 werden feuchtigkeitsunempfindliche Ruthenium-Katalysatoren beschrieben, die sich aufgrund ihrer hohen Reaktivität jedoch nicht für das RIM-Verfahren eignen.In WO 96/16100 and WO 96/20235 moisture-insensitive Ruthenium catalysts are described, but because of their high reactivity not suitable for the RIM process.

Aufgabe der vorliegenden Erfindung war es, ein gegen Luft und Feuchtigkeit stabiles 2-Komponenten-Katalysatorsystem für die ringöffnende Metathesepolymerisation mit ausreichender Reaktivität für den RIM-Prozess bereitzustellen.The object of the present invention was to be stable against air and moisture 2-component catalyst system for ring-opening metathesis polymerization with to provide sufficient reactivity for the RIM process.

Es wurde nun gefunden, dass bestimmte Ruthenium-Komplexe und tertiäre Phosphine mit sekundären Alkyl- oder Cycloalkylgruppen ein geeignetes lagerstabiles 2-Komponenten-System bilden, welches gehärtete Produkte mit ausgezeichneten Eigenschaften, insbesondere hoher Wärmestabilität, hoher Zähigkeit und mechanischer Festigkeit, liefert.It has now been found that using certain ruthenium complexes and tertiary phosphines secondary alkyl or cycloalkyl groups a suitable storage-stable 2-component system form which hardened products with excellent properties, especially high thermal stability, high toughness and mechanical strength.

Gegenstand der vorliegenden Anmeldung ist somit ein Katalysatorsystem für die ringöffnende Metathesepolymerisation bestehend aus mindestens zwei Komponenten (a) und (b), wobei

  • (a) eine Ruthenium-Verbindung der Formel I oder II ist RuX2(L1)m(L2)n(L3)o(L4)p ARuX2(L1)r(L2)s worin L1, L2, L3 und L4 unabhängig voneinander ein C1-C18-Alkylcyanid, ein C6-C24-Aralkylcyanid, ein tertiäres Amin, ein tertiäres Phosphin, welches keine an das Phosphoratom gebundenen sekundären Alkyl- oder Cycloalkylreste enthält, oder ein Phosphit darstellen, X für Halogen steht, A ein Aren bedeutet, m, n, o und p ganze Zahlen von 0 bis 4 darstellen, wobei gilt 2 ≤ m + n + o + p ≤ 4, r und s ganze Zahlen von 0 bis 2 darstellen, wobei gilt 1 ≤ r + s ≤ 2, und
  • (b) ein tertiäres Phosphin mit mindestens einem am Phosphoratom gebundenen sekundären Alkyl- oder Cycloalkylrest darstellt.
    • The present application thus relates to a catalyst system for ring-opening metathesis polymerization consisting of at least two components (a) and (b), wherein
  • (a) is a ruthenium compound of formula I or II RuX 2 (L 1 ) m (L 2 ) n (L 3 ) o (L 4 ) p ARuX 2 (L 1 ) r (L 2 ) s wherein L 1 , L 2 , L 3 and L 4 independently of one another are a C 1 -C 18 alkyl cyanide, a C 6 -C 24 aralkyl cyanide, a tertiary amine, a tertiary phosphine which has no secondary alkyl or bonded to the phosphorus atom Contains cycloalkyl radicals or represent a phosphite, X represents halogen, A represents an arene, m, n, o and p represent integers from 0 to 4, where 2 ≤ m + n + o + p ≤ 4, r and s represent integers from 0 to 2, where 1 ≤ r + s ≤ 2, and
  • (b) represents a tertiary phosphine with at least one secondary alkyl or cycloalkyl radical bonded to the phosphorus atom.

    • Die Ruthenium-Verbindungen der Formeln I oder II können nach bekannten Verfahren durch Umsetzung von Rutheniumdihalogeniden mit den entsprechenden Arenen, Nitrilen, Aminen, Phosphinen oder Phosphiten hergestellt werden.The ruthenium compounds of the formulas I or II can be prepared by known methods Implementation of ruthenium dihalides with the corresponding arenes, nitriles, amines, Phosphines or phosphites are produced.

    Als Liganden L1 bis L4 geeignete C1-C18-Alkylcyanide sind beispielsweise Acetonitril, Propionitril, n-Butyronitril, Isobutyronitril, Pivalonitril, neo-Pentylcyanid, Valeronitril, Capronitril, n-Heptylcyanid, n-Octylcyanid, n-Nonylcyanid und n-Decylcyanid. Beispiele für geeignete C6-C24-Aralkylcyanide sind Phenylacetonitril, 3-Phenylpropionitril, 4-Phenylbutyronitril und Naphthylacetonitril.Suitable C 1 -C 18 alkyl cyanides as ligands L 1 to L 4 are, for example, acetonitrile, propionitrile, n-butyronitrile, isobutyronitrile, pivalonitrile, neo-pentyl cyanide, valeronitrile, capronitrile, n-heptyl cyanide, n-octyl cyanide and n-nonyl cyanide -Decylcyanid. Examples of suitable C 6 -C 24 aralkyl cyanides are phenylacetonitrile, 3-phenylpropionitrile, 4-phenylbutyronitrile and naphthylacetonitrile.

    Tertiäre Amine als Liganden L1 bis L4 sind zum Beispiel Trimethylamin, Triethylamin, Tri-npropylamin, Triisopropylamin, Tri-n-butylamin, Triisobutylamin, Tri-tert.-butylamin, Benzyldimethylamin, Triphenylamin, Tricyclohexylamin, Phenyldimethylamin, Phenyldiethylamin, Cyclohexyldimethylamin, Cyclohexyldiethylamin, Urotropin, Triethylendiamin, N-Methylpiperidin und N-Ethylpiperidin.Tertiary amines as ligands L 1 to L 4 are, for example, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-tert.-butylamine, benzyldimethylamine, triphenylamine, tricyclohexylamine, phenyldimethylamine, cyclyldietylamine amine, phenyldietylamine amine , Urotropin, triethylenediamine, N-methylpiperidine and N-ethylpiperidine.

    L1 bis L4 als tertiäres Phosphin kann beispielsweise Trimethylphosphin, Triethylphosphin, Trin-propylphosphin, Tri-n-butylphosphin, Triphenylphosphin, Methyldiphenylphosphin, Dimethylphenylphosphin, Tri-n-octylphosphin, Tritolylphosphin oder eine Verbindung der Formel lll sein

    Figure 00030001
    worin R für C1-C18-Alkyl, C5-C14-Aryl oder C6-C24-Aralkyl steht.
    In der Formel lll können die Alkylgruppen geradkettig oder verzweigt sein und enthalten bevorzugt 1 bis 12, besonders bevorzugt 1 bis 8 und insbesondere bevorzugt 1 bis 4 C-Atome.
    Alkyl umfaßt beispielsweise Methyl, Ethyl, Isopropyl, n-Propyl, n-Butyl, Isobutyl, sek.-Butyl, tert.-Butyl sowie die verschiedenen isomeren Pentyl-, Hexyl-, Heptyl-, Octyl-, Nonyl-, Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl-, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecyl- und Eicosylgruppen.
    R als Aryl enthält bevorzugt 6 bis 10 C-Atome. Es kann sich beispielsweise um Phenyl, Tolyl, Pentalinyl, Indenyl, Naphtyl, Azulinyl und Anthryl handeln.
    R als Aralkyl enthält bevorzugt 7 bis 12 C-Atome und besonders bevorzugt 7 bis 10 C-Atome. Es kann sich zum Beispiel um Benzyl, Phenethyl, 3-Phenylpropyl, α-Methylbenzyl, 4-Phenylbutyl und α,α-Dimethylbenzyl handeln.L 1 to L 4 as tertiary phosphine can be, for example, trimethylphosphine, triethylphosphine, trin-propylphosphine, tri-n-butylphosphine, triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tri-n-octylphosphine, tritolylphosphine or a compound of the formula III
    Figure 00030001
    wherein R is C 1 -C 18 alkyl, C 5 -C 14 aryl or C 6 -C 24 aralkyl.
    In formula III, the alkyl groups can be straight-chain or branched and preferably contain 1 to 12, particularly preferably 1 to 8 and particularly preferably 1 to 4 carbon atoms.
    Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups.
    R as aryl preferably contains 6 to 10 carbon atoms. It can be, for example, phenyl, tolyl, pentalinyl, indenyl, naphthyl, azulinyl and anthryl.
    R as aralkyl preferably contains 7 to 12 carbon atoms and particularly preferably 7 to 10 carbon atoms. For example, it can be benzyl, phenethyl, 3-phenylpropyl, α-methylbenzyl, 4-phenylbutyl and α, α-dimethylbenzyl.

    Geeignete Phosphite als Liganden L1 bis L4 sind beispielsweise Trimethylphosphit, Triethylphosphit, Tri-n-propylphosphit, Triisopropylphosphit, Tri-n-butylphosphit, Triphenylphosphit, Methyldiphenylphosphit, Dimethylphenylphosphit, Tri-n-octylphosphit, Tritolylphosphit oder Tris(p-nonylphenyl)phosphit oder Verbindungen der oben angegebenen Formel III.Suitable phosphites as ligands L 1 to L 4 are, for example, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triphenyl phosphite, methyldiphenyl phosphite, dimethylphenyl phosphite, tri-n-octyl phosphite, tritolyl phosphite or tritolyl phosphite or tritolyl phosphite or tritolyl phosphite or tritolyl phosphite or compounds of formula III given above.

    X steht in den Formeln I oder II für Fluor, Chlor, Brom oder lod, insbesondere für Chlor.X in the formulas I or II represents fluorine, chlorine, bromine or iodine, in particular chlorine.

    Der Begriff "Aren" steht ganz allgemein für aromatische Verbindungen. In den Formeln II und lll steht A vorzugsweise für unsubstituierte oder mit OH, C1-C4-Alkyl, C1-C4-Alkoxy, C6-C12-Aryl oder Halogen substituierte monocyclische, polycyclische oder kondensierte Arene mit 6 bis 24, bevorzugt 6 bis 18 und besonders bevorzugt 6 bis 12 C-Atomen. The term "arene" generally stands for aromatic compounds. In the formulas II and III, A preferably represents unsubstituted or substituted with OH, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 6 -C 12 aryl or halogen monocyclic, polycyclic or condensed arenes with 6 to 24, preferably 6 to 18 and particularly preferably 6 to 12 carbon atoms.

    Einige Beispiele für Arene und Heteroarene sind Benzol, Toluol, o-Xylol, p-Xylol, Mesitylen, Ethylbenzol, Cumol, 1,3,5-Triisopropylbenzol, p-Cymol, Durol, Hexamethylbenzol, Naphthalin, Biphenyl, Diphenylmethan, Anthracen, Acenaphthen, Fluoren, Phenanthren, Pyren, Chrysen, Fluoranthren, Furan, Thiophen, Pyrrol, Pyridin, γ-Pyran, γ-Thiopyran, Pyrimidin, Pyrazin, Indol, Cumaron, Thionaphthen, Carbazol, Dibenzofuran, Benzthiophen, Dibenzothiophen, Pyrazol, Imidazol, Benzimidazol, Oxazol, Thiazol, Isoxazol, Isothiazol, Chinolin, Isochinolin, Acridin, Chromen, Phenazin, Phenoxazin, Phenothiazin, Triazine, Thianthren und Purin. Bevorzugte Arene und Heteroarene sind unsubstituiertes oder substituiertes Benzol, Naphthalin, Thiophen und Benzthiophen.Some examples of arenes and heteroarenes are benzene, toluene, o-xylene, p-xylene, mesitylene, Ethylbenzene, cumene, 1,3,5-triisopropylbenzene, p-cymene, durol, hexamethylbenzene, Naphthalene, biphenyl, diphenylmethane, anthracene, acenaphthene, fluorene, phenanthrene, Pyrene, chrysene, fluoranthrene, furan, thiophene, pyrrole, pyridine, γ-pyran, γ-thiopyran, Pyrimidine, pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran, benzthiophene, Dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazole, isothiazole, Quinoline, isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazines, Thianthrene and purine. Preferred arenes and heteroarenes are unsubstituted or substituted benzene, naphthalene, thiophene and benzthiophene.

    Als Komponente (b) des erfindungsgemäßen Katalysatorsystems eignen sich im Prinzip alle tertiären Phosphine, die mindestens eine direkt an das Phosphoratom gebundene sekundäre Alkyl- oder Cycloalkylgruppe aufweisen.
    Als Beispiele für solche Phosphine seien Isopropyldimethylphosphin, Diisopropylmethylphosphin, lsopropyldiethylphosphin, Diisopropylethylphosphin, lsopropyldiphenylphosphin, Diisopropylphenylphosphin, Triisopropylphosphin, Tri-secbutylphosphin, Tris(1-Methylbutyl)phosphin, Tris(1-Ethylbutyl)phosphin, Cyclohexyldimethylphosphin, Dicyclohexylmethylphosphin und Tricyclohexylphosphin genannt.    In principle, all tertiary phosphines which have at least one secondary alkyl or cycloalkyl group bonded directly to the phosphorus atom are suitable as component (b) of the catalyst system according to the invention.
    Examples of such phosphines are isopropyldimethylphosphine, diisopropylmethylphosphine, isopropyldiethylphosphine, diisopropylethylphosphine, isopropyldiphenylphosphine, diisopropylphenylphosphine, tri-secylhexylphosphine, tris (1-methylbutyl) phosphine

    In einer bevorzugten Ausführungsform der Erfindung ist Komponente (a) eine Verbindung der Formel II, worin A für Benzol, Toluol, o-Xylol, p-Xylol, Mesitylen, Ethylbenzol, Cumol, 1,3,5-Triisopropylbenzol, p-Cymol, Durol, Hexamethylbenzol, Naphthalin, Biphenyl oder Diphenylmethan steht.In a preferred embodiment of the invention, component (a) is a compound of the formula II, in which A is benzene, toluene, o-xylene, p-xylene, mesitylene, ethylbenzene, cumene, 1,3,5-triisopropylbenzene, p-cymene, durol, hexamethylbenzene, naphthalene, biphenyl or Diphenylmethane stands.

    Weiterhin bevorzugt als Komponente (a) ist eine Verbindung der Formel I oder II, worin ein oder mehrere Liganden L1 bis L4 Acetonitril, Propionitril, n-Butyronitril, Valeronitril oder Capronitril sind.Also preferred as component (a) is a compound of the formula I or II, in which one or more ligands L 1 to L 4 are acetonitrile, propionitrile, n-butyronitrile, valeronitrile or capronitrile.

    Bevorzugt als Komponente (a) sind ausserdem Verbindungen der Formel I oder II, worin ein oder mehrere Liganden L1 bis L4 Triphenylphosphin, Methyldiphenylphosphin, Dimethylphenylphosphin, Tri(n-butyl)phosphin, Tri(n-octyl)phosphin, Trimethylphosphit, Triisopropylphosphit, Triphenylphosphit, Tris(p-nonylphenyl)phosphit oder eine Verbindung der Formel lll sind

    Figure 00050001
    worin R für C1-C18-Alkyl, C5-C14-Aryl oder C6-C24-Aralkyl steht.Preferred as component (a) are also compounds of the formula I or II, in which one or more ligands L 1 to L 4 triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tri (n-butyl) phosphine, tri (n-octyl) phosphine, trimethylphosphite, triisopropylphosphite , Triphenyl phosphite, tris (p-nonylphenyl) phosphite or a compound of formula III
    Figure 00050001
    wherein R is C 1 -C 18 alkyl, C 5 -C 14 aryl or C 6 -C 24 aralkyl.

    Besonders bevorzugt als Komponente (a) ist eine Verbindung der Formel II, worin A für p-Cymol, r für 2 und L1 für Butyronitril oder Capronitril steht.A particularly preferred component (a) is a compound of the formula II in which A is p-cymene, r is 2 and L 1 is butyronitrile or capronitrile.

    Insbesondere bevorzugt als Komponente (a) ist weiterhin eine Verbindung der Formel II, worin A für p-Cymol, r für 1, s für 0 und L1 für Triphenylphosphit, Tris(p-nonylphenyl)phosphit oder 2,4,8,10-Tetrakis(1,1-dimethylethyl)-6-methoxy-dibenzo[d,f][1,3,2]dioxaphosphepin steht.Also particularly preferred as component (a) is a compound of the formula II in which A is p-cymene, r is 1, s is 0 and L 1 is triphenyl phosphite, tris (p-nonylphenyl) phosphite or 2,4,8,10 -Tetrakis (1,1-dimethylethyl) -6-methoxy-dibenzo [d, f] [1,3,2] dioxaphosphepine.

    Als Komponente (b) wird vorzugsweise Triisopropylphosphin oder Tricyclohexylphosphin verwendet.Triisopropylphosphine or tricyclohexylphosphine is preferably used as component (b) used.

    Beide Komponenten (a) und (b) sind nicht reaktiv gegenüber gespannten Cycloolefinen, d.h. Mischungen enthaltend ein Cycloolefin und Komponente (a) bzw. ein Cycloolefin und Komponente (b) sind bei Raumtemperatur über mehrere Monate lagerstabil. Erst beim Mischen der beiden Komponenten entsteht ein Produkt, das als Katalysator für die ringöffnende Metathesepolymerisation wirkt. Das erfindungsgemäße Zwei-Komponenten-System eignet sich daher besonders für das RIM-Verfahren, da das polymerisierbare Cycloolefin vor der Verarbeitung in zwei Portionen geteilt werden kann, die mit den entsprechenden Mengen der Komponenten (a) und (b) versetzt werden. Beim Vermischen der beiden Portionen und Einspritzen in die vorgewärmte Form polymersisiert das Gemisch dann sehr rasch und bildet gehärtete Produkte mit guten mechanischen Eigenschaften.Both components (a) and (b) are not reactive towards strained cycloolefins, i.e. Mixtures containing a cycloolefin and component (a) or a cycloolefin and Component (b) are stable in storage at room temperature for several months. Not until Mixing the two components creates a product that acts as a catalyst for the ring-opening metathesis polymerization works. The two-component system according to the invention is therefore particularly suitable for the RIM process, since the polymerisable Cycloolefin can be divided into two portions prior to processing, using the appropriate amounts of components (a) and (b) are added. When mixing the mixture is polymerized by the two portions and injection into the preheated mold then very quickly and forms hardened products with good mechanical properties.

    Gegenstand der vorliegenden Erfindung ist daher auch ein härtbares 2-Komponenten-System bestehend aus mindestens zwei Komponenten (c) und (d), wobei

  • (c) eine Mischung aus 90,0-99,999 Gew.-%, vorzugsweise 95,0- 99,9 Gew.-%, insbesondere 98,0-99,6 Gew.-%, eines gespannten Cycloolefins und 0,001-10,0 Gew.-%, vorzugsweise 0,1- 5,0 Gew.-%, insbesondere 0,4- 2,0 Gew.-%, der oben angegebenen Komponente (a) ist, und
  • (d) eine Mischung aus 90,0-99,999 Gew.-%, vorzugsweise 95,0- 99,9 Gew.-%, insbesondere 98,0-99,6 Gew.-%, eines gespannten Cycloolefins und 0,001-10,0 Gew.-%, vorzugsweise 0,1- 5,0 Gew.-%, insbesondere 0,4- 2,0 Gew.-%, der oben angegebenen Komponente (b) ist.
    • The present invention therefore also relates to a curable 2-component system consisting of at least two components (c) and (d), wherein
  • (c) a mixture of 90.0-99.999% by weight, preferably 95.0-99.9% by weight, in particular 98.0-99.6% by weight, of a strained cycloolefin and 0.001-10, 0% by weight, preferably 0.1-5.0% by weight, in particular 0.4-2.0% by weight, of component (a) given above, and
  • (d) a mixture of 90.0-99.999% by weight, preferably 95.0-99.9% by weight, in particular 98.0-99.6% by weight, of a strained cycloolefin and 0.001-10, 0% by weight, preferably 0.1-5.0% by weight, in particular 0.4-2.0% by weight, of the above-mentioned component (b).

    • Unter gespannten Cycloolefinen sind im Rahmen der vorliegenden Erfindung alle Cycloolefine mit Ausnahme des Cyclohexens und seiner Derivate, die nicht mit der ringöffnenden Metathese polymerisiert werden können, zu verstehen.Within the scope of the present invention, all strained cycloolefins are Cycloolefins with the exception of cyclohexene and its derivatives, which are not compatible with the ring-opening metathesis can be polymerized to understand.

    Bei den gespannten Cycloolefinen kann es sich um monocyclische oder polycyclische kondensierte bzw. überbrückte Ringsysteme, zum Beispiel mit zwei bis vier Ringen, handeln, die unsubstituiert oder substituiert sind und ein oder mehrere Heteroatome, wie zum Beispiel O, S, N oder Si, in einem oder mehreren Ringen und/oder kondensierte aromatische oder heteroaromatische Ringe, wie zum Beispiel o-Phenylen, o-Naphthylen, o-Pyridinylen oder o-Pyrimidinylen, enthalten können. Die einzelnen cyclischen Ringe können 3 bis 16, bevorzugt 3 bis 12 und besonders bevorzugt 3 bis 8 Ringglieder enthalten. Die gespannten Cycloolefine können weitere nichtaromatische Doppelbindungen enthalten, je nach Ringgrösse bevorzugt 2 bis 4 solcher zusätzlicher Doppelbindungen.The strained cycloolefins can be monocyclic or polycyclic act as condensed or bridged ring systems, for example with two to four rings, which are unsubstituted or substituted and one or more heteroatoms, such as O, S, N or Si, in one or more rings and / or condensed aromatic or heteroaromatic rings, such as, for example, o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene, can contain. The individual cyclic rings can be 3 to 16, preferably Contain 3 to 12 and particularly preferably 3 to 8 ring members. The tense Cycloolefins can contain other non-aromatic double bonds, depending on Ring size preferably 2 to 4 such additional double bonds.

    Wenn die gespannten Cycloolefine mehr als eine Doppelbindung enthalten, zum Beispiel 2 bis 4 Doppelbindungen, können sich abhängig von den Reaktionsbedingungen, dem gewählten Monomer und der Katalysatormenge, auch vemetzte Polymerisate bilden.If the strained cycloolefins contain more than one double bond, for example 2 up to 4 double bonds, depending on the reaction conditions, the selected monomer and the amount of catalyst, also form crosslinked polymers.

    Bevorzugte Cycloolefine sind Diels-Alder-Addukte von Cyclopentadien.Preferred cycloolefins are Diels-Alder adducts of cyclopentadiene.

    Geeignete Diels-Alder-Addukte von Cyclopentadien sind beispielsweise die folgenden Verbindungen:

    Figure 00070001
    Figure 00070002
    Figure 00070003
    Figure 00070004
    Figure 00070005
    Figure 00070006
    Figure 00070007
    Figure 00080001
    Figure 00080002
    Figure 00080003
    Figure 00080004
    Suitable Diels-Alder adducts of cyclopentadiene are, for example, the following compounds:
    Figure 00070001
    Figure 00070002
    Figure 00070003
    Figure 00070004
    Figure 00070005
    Figure 00070006
    Figure 00070007
    Figure 00080001
    Figure 00080002
    Figure 00080003
    Figure 00080004

    Bevorzugte Diels-Alder-Addukte sind Norbornen (1), Norbomadien (6), Cyclohexenylnorbornen (25), Tetracyclododecen (14), Methyltetracyclododecen (11) und insbesondere Dicyclopentadien (18).Preferred Diels-Alder adducts are norbornene (1), norbomadiene (6), Cyclohexenylnorbornene (25), Tetracyclododecen (14), Methyltetracyclododecen (11) and especially dicyclopentadiene (18).

    Die gewünschte Viskosität des härtbaren Gemisches kann durch Zusatz von thermoplastischen Materialien eingestellt werden. Beispiele für geeignete Thermoplasten sind Polystyrol, Polynorbornen (z.B. Norsorex® NS der Fa. Nippon Zeon), hydrierte Polynorbornenderivate (z.B. Zeonex® der Fa. Nippon Zeon), Polycycloocten (z.B. Vestenamer® der Fa. Hüls) und Polybutadien.The desired viscosity of the curable mixture can be achieved by adding thermoplastic materials can be adjusted. Examples of suitable thermoplastics are polystyrene, polynorbornene (e.g. Norsorex® NS from Nippon Zeon), hydrogenated Polynorborn derivatives (e.g. Zeonex® from Nippon Zeon), polycyclooctene (e.g. Vestenamer® from Hüls) and polybutadiene.

    Weiterhin können die härtbaren Mischungen Zähigkeitsvermittler ("Toughener") enthalten, wie zum Beispiel Core/Shell-Polymere oder die dem Fachmann als "Rubber Toughener" bekannten Elastomere oder Elastomere enthaltende Pfropfpolymere.
    Geeignete Zähigkeitsvermittler sind beispielsweise in der EP-A-449 776 beschrieben.     Furthermore, the curable mixtures can contain tougheners, such as, for example, core / shell polymers or the elastomers or graft polymers containing those known to the person skilled in the art as "rubber tougers".
    Suitable tougheners are described, for example, in EP-A-449 776.

    Zur Verbesserung der elektrischen Eigenschaften (Dielektrizitätskonstante, Verlustfaktor) können den härtbaren Mischungen Silane, wie z.B. die von der Fa. Osi Specialties unter der Bezeichnung Silquest® Silan angebotenen Verbindungen, zugesetzt werden. Geeignete Silane sind beispielsweise Octyltriethoxysilan, Methyltriethoxysilan, Vinyltriethoxysilan, Methyltrimethoxysilan, Vinyltrimethoxysilan, γ-Aminopropyltrimethoxysilan und γ-Glycidyloxypropyltrimethoxysilan.To improve the electrical properties (dielectric constant, loss factor) can be added to the curable mixtures silanes, e.g. from Osi Specialties under the Description Silquest® Silane offered compounds can be added. suitable Silanes are, for example, octyltriethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, Methyltrimethoxysilane, vinyltrimethoxysilane, γ-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

    Neben den oben erwähnten Additiven können die erfindungsgemäßen Zusammensetzungen weitere übliche Zusatzstoffe enthalten, wie z.B. Antioxidantien, Lichtschutzmittel, Weichmacher, Farbstoffe, Füllstoffe, Pigmente, Thixotropiemittel, Entschäumer, Antistatika, Gleitmittel und Entformungshilfsmittel.In addition to the additives mentioned above, the compositions according to the invention can contain other common additives, e.g. Antioxidants, light stabilizers, Plasticizers, dyes, fillers, pigments, thixotropic agents, defoamers, antistatic agents, Lubricants and mold release agents.

    Zur Steigerung der katalytischen Aktivität kann der Komponente (b) eine geringe Menge eines Alkins, wie beispielsweise 1-Heptin, 1-Octin, 1-Decin oder Phenylethin, zugesetzt werden.To increase the catalytic activity, component (b) may contain a small amount an alkyne such as 1-heptin, 1-octyne, 1-decyne or phenylethine become.

    Einen weiteren Erfindungsgegenstand bildet ein Verfahren zur Herstellung eines Metathesepolymerisats, dadurch gekennzeichnet, dass eine Zusammensetzung enthaltend die Komponenten (c) und (d) auf eine Temperatur >40 °C erwärmt wird.A further subject of the invention is a method for producing a Metathesis polymer, characterized in that containing a composition components (c) and (d) are heated to a temperature> 40 ° C.

    Zweckmässig wird das erfindungsgemäße Verfahren bei einer Temperatur von mindestens 60°C durchgeführt. Insbesondere wird das erfindungsgemäße Verfahren bei Temperaturen von 60 bis 300 °C, besonders bevorzugt bei 60 bis bis 200 °C und insbesondere bevorzugt bei 70 bis 160 °C, durchgeführt. Nach der Polymerisation kann es vorteilhaft sein, das Gemisch bei erhöhten Temperaturen, zum Beispiel 80 bis 200 °C, nachzutempern.The method according to the invention is expedient at a temperature of at least 60 ° C carried out. In particular, the inventive method at temperatures from 60 to 300 ° C, particularly preferably at 60 to 200 ° C and particularly preferred at 70 to 160 ° C performed. After the polymerization, it may be advantageous that Post-temper mixture at elevated temperatures, for example 80 to 200 ° C.

    Die nach dem erfindungsgemäßen Verfahren hergestellten Metathese-Polymerisate können Homopolymere, Copolymere mit statistischer Verteilung der Struktureinheiten, Pfropfpolymere, Blockpolymere oder vemetzte Polymere sein. Die Polymere können ein mittleres Molekulargewicht von 500 bis zu 2'000'000 Dalton, vorzugsweise 1000 bis 1'000'000 Dalton (bestimmt mittels Gelpermeationschromatographie) aufweisen. The metathesis polymers prepared by the process according to the invention can Homopolymers, copolymers with statistical distribution of the structural units, Graft polymers, block polymers or cross-linked polymers. The polymers can be a average molecular weight of 500 to 2,000,000 daltons, preferably 1000 to Have 1,000,000 daltons (determined by gel permeation chromatography).

    Die nach dem erfindungsgemäßen Verfahren hergestellten Polymerisate zeichnen sich vor allem durch eine hohe Wärmestabilität, hohe Zähigkeit und mechanische Festigkeit sowie durch hervorragende elektrische Eigenschaften (niedrige Dielektrizitätskonstante, niedriger Verlustfaktor bzw. tanδ-Wert) aus und eignen sich für Anwendungen in der Vakuum-Gießtechnologie, als Gießharze, lmprägnierharze und insbesondere als Umhüllungsmaterial für elektrische und elektronische Bauteile.The polymers prepared by the process according to the invention stand out all thanks to high thermal stability, high toughness and mechanical strength as well due to excellent electrical properties (low dielectric constant, lower Loss factor or tan δ value) and are suitable for applications in vacuum casting technology, as casting resins, impregnating resins and in particular as coating material for electrical and electronic components.

    Einen weiteren Erfindungsgegenstand bildet ein Verfahren zur Herstellung von Formkörpern, dadurch gekennzeichnet, dass ein härtbares 2-Komponenten-System enthaltend die oben angegebenen Komponenten (c) und (d) nach dem RIM-Verfahren in eine Form eingebracht und gehärtet wird.Another object of the invention is a process for the production of moldings, characterized in that a curable 2-component system containing the above specified components (c) and (d) introduced into a mold by the RIM method and is hardened.

    Die Verwendung eines härtbaren 2-Komponenten-Systems enthaltend die oben angegebenen Komponenten (c) und (d) als Umhüllungsmaterial für elektrische oder elektronische Bauteile stellt einen weiteren Erfindungsgegenstand dar.The use of a curable 2-component system containing the above specified components (c) and (d) as wrapping material for electrical or Electronic components represent a further subject of the invention.

    Beispiele:Examples:

    Das in den nachfolgenden Beispielen verwendete Dicyclopentadien wird ca. 15 Minuten bei Raumtemperatur unter Vakuum (3 mbar) entgast und anschließend unter Stickstoff aufbewahrt.
    [(p-Cymol)RuCl2{2,4,8,10-tetrakis(1,1-dimethylethyl)-6-methoxy-dibenzo[d,f][1,3,2]dioxaphosphepin}], [(p-Cymol)RuCl2(Triphenylphosphit)] und [(p-Cymol)RuCl2{Tris(pnonylphenyl)phosphit}] werden hergestellt durch Zugabe von einem Äquivalent des entsprechenden Phosphits zu einer Lösung von [(p-Cymol)RuCl2]2 in Methylenchlorid. Die reinen Produkte werden durch Abdestillieren des Lösungsmittels und anschließendes Waschen mit Hexan in nahezu quantitativer Ausbeute isoliert.    The dicyclopentadiene used in the examples below is degassed for about 15 minutes at room temperature under vacuum (3 mbar) and then stored under nitrogen.
    [(p-Cymol) RuCl 2 {2,4,8,10-tetrakis (1,1-dimethylethyl) -6-methoxy-dibenzo [d, f] [1,3,2] dioxaphosphepine}], [(p -Cymol) RuCl 2 (triphenylphosphite)] and [(p-cymene) RuCl 2 {tris (pnonylphenyl) phosphite}] are prepared by adding one equivalent of the corresponding phosphite to a solution of [(p-cymene) RuCl 2 ] 2 in methylene chloride. The pure products are isolated by distilling off the solvent and then washing with hexane in almost quantitative yield.

    Folgende Abkürzungen werden verwendet:

    DCPD:
    Dicyclopentadien (wenn nicht anders angegeben: 97 % Fa. BF Goodrich)
    DSC:
    Differential Scanning Calorimetry
    TGA
    Thermogravimetrische Analyse
    Tg:
    Glasübergangstemperatur (gemessen mittels DSC, Aufheizrate: 10 °C/min)
    The following abbreviations are used:
    DCPD:
    Dicyclopentadiene (unless otherwise stated: 97% from BF Goodrich)
    DSC:
    Differential scanning calorimetry
    TGA
    Thermogravimetric analysis
    T g :
    Glass transition temperature (measured by DSC, heating rate: 10 ° C / min)

    Beispiel 1example 1

    Eine Lösung von 25mg [(p-Cymol)RuCl2]2 und 13µl Butyronitril in 5 ml DCPD wird 30 min bei 80°C gerührt. Die so hergestellte Lösung von [(p-Cymol)RuCl2(Butyronitril)2] wird mit 2,9 ml einer Lösung von Tricyclohexylphosphin in DCPD (1 Gew.%) versetzt und anschließend ausgehärtet (16 h/80 °C; 2 h/ 120 °C). Dabei wird ein gelbes, festes Polymer (Tg = 33 °C) erhalten.A solution of 25 mg [(p-cymene) RuCl 2 ] 2 and 13 μl butyronitrile in 5 ml DCPD is stirred at 80 ° C. for 30 min. The solution of [(p-cymene) RuCl 2 (butyronitrile) 2 ] thus prepared is mixed with 2.9 ml of a solution of tricyclohexylphosphine in DCPD (1% by weight) and then hardened (16 h / 80 ° C; 2 h / 120 ° C). A yellow, solid polymer (T g = 33 ° C.) is obtained.

    Beispiel 2Example 2

    Eine Lösung von 25mg [(p-Cymol)RuCl2]2 und 20µl Capronitril in 5 ml DCPD wird 30 min bei 80°C gerührt. Die so hergestellte Lösung von [(p-Cymol)RuCl2(Capronitril)2] wird mit 2,9 ml einer Lösung von Tricyclohexylphosphin in DCPD (1 Gew.%) versetzt und anschließend ausgehärtet (16 h/80°C; 2 h/ 120°C). Dabei wird ein gelbes, festes Polymer (Tg = 40 °C) erhalten.A solution of 25 mg [(p-cymene) RuCl 2 ] 2 and 20 μl capronitrile in 5 ml DCPD is stirred at 80 ° C. for 30 min. The solution of [(p-cymene) RuCl 2 (capronitrile) 2 ] prepared in this way is mixed with 2.9 ml of a solution of tricyclohexylphosphine in DCPD (1% by weight) and then cured (16 h / 80 ° C; 2 h / 120 ° C). A yellow, solid polymer (T g = 40 ° C.) is obtained.

    Beispiel 3Example 3

    Eine Lösung von 61 mg [(p-Cymol)RuCl2{2,4,6,10-tetrakis(1,1-dimethylethyl)-6-methoxydibenzo[d,f][1,3,2]dioxaphosphepin}] in 5 ml DCPD wird mit 2,9 ml einer Lösung von Tricyclohexylphosphin in DCPD (1 Gew.%) versetzt und anschließend ausgehärtet (16 h/80 °C; 3,5 h/120 °C). Dabei wird ein grünlich-braunes, festes Polymer (Tg = 31 °C) erhalten.A solution of 61 mg [( p- Cymol) RuCl 2 {2,4,6,10-tetrakis (1,1-dimethylethyl) -6-methoxydibenzo [d, f] [1,3,2] dioxaphosphepine}] in 5 ml of DCPD is mixed with 2.9 ml of a solution of tricyclohexylphosphine in DCPD (1% by weight) and then cured (16 h / 80 ° C; 3.5 h / 120 ° C). A greenish-brown, solid polymer (T g = 31 ° C) is obtained.

    Beispiel 4Example 4

    Eine Lösung von 31 mg [(p-Cymol)RuCl2(Triphenylphosphit)] in 5 ml DCPD wird mit 14 mg Tricyclohexylphosphin und 7 µl Phenylacetylen versetzt und anschließend ausgehärtet (55 h/80 °C; 2 h/ 120 °C). Dabei wird ein braunes, festes Polymer (Tg = 103 °C) erhalten.A solution of 31 mg [(p-cymene) RuCl 2 (triphenylphosphite)] in 5 ml DCPD is mixed with 14 mg tricyclohexylphosphine and 7 μl phenylacetylene and then hardened (55 h / 80 ° C; 2 h / 120 ° C). This gives a brown, solid polymer (T g = 103 ° C).

    Beispiel 5Example 5

    Eine Lösung von 31 mg [(p-Cymol)RuCl2(Triphenylphosphit)] in 5 ml DCPD wird mit 14 mg Tricyclohexylphosphin und 5 µl Phenylacetylen versetzt und anschließend ausgehärtet (55 h/80 °C; 2 h/ 120 °C). Dabei wird ein braunes, festes Polymer (Tg = 103 °C) erhalten.A solution of 31 mg [(p-cymene) RuCl 2 (triphenylphosphite)] in 5 ml DCPD is mixed with 14 mg tricyclohexylphosphine and 5 µl phenylacetylene and then hardened (55 h / 80 ° C; 2 h / 120 ° C). This gives a brown, solid polymer (T g = 103 ° C).

    Beispiel 6Example 6

    Eine Lösung von 31 mg [(p-Cymol]RuCl2(Triphenylphosphit]] in 5 ml DCPD wird mit 14 mg Tricyclohexylphosphin und 5 µl Phenylacetylen versetzt und anschließend ausgehärtet (1,5 h/100 °C; 2,5 h/ 120 °C; 15 h/150 °C). Dabei wird ein hartes, gelbes Polymer (Tg = 146 °C) erhalten.A solution of 31 mg [(p-cymene] RuCl 2 (triphenylphosphite]) in 5 ml DCPD is mixed with 14 mg tricyclohexylphosphine and 5 μl phenylacetylene and then hardened (1.5 h / 100 ° C; 2.5 h / 120 ° C; 15 h / 150 ° C), giving a hard, yellow polymer (T g = 146 ° C).

    Beispiel 7Example 7

    Eine Lösung von 31 mg [(p-Cymol)RuCl2(Triphenylphosphit)] in 5 ml DCPD wird mit 14 mg Tricyclohexylphosphin und 5 µl Phenylacetylen versetzt und anschließend ausgehärtet (1,5 h/80 °C; 2,5 h/ 100 °C; 15 h/120 °C). Dabei wird ein hartes, braunes Polymer (Tg = 146 °C) erhalten.A solution of 31 mg [(p-cymene) RuCl 2 (triphenylphosphite)] in 5 ml DCPD is mixed with 14 mg tricyclohexylphosphine and 5 µl phenylacetylene and then hardened (1.5 h / 80 ° C; 2.5 h / 100 ° C; 15 h / 120 ° C). A hard, brown polymer (T g = 146 ° C) is obtained.

    Beispiel 8Example 8

    Eine Lösung von 50 mg [(p-Cymol)RuCl2{tris(p-nonylphenyl)phosphit}] in 5 ml DCPD wird mit 14 mg Tricyclohexylphosphin und 5 µl Phenylacetylen versetzt und anschließend ausgehärtet (2 h/80 °C; 2 h/ 120 °C; 14 h/140 °C). Dabei wird ein hartes, braunes Polymer (Tg = 95 °C) erhalten.A solution of 50 mg [(p-cymene) RuCl 2 {tris (p-nonylphenyl) phosphite}] in 5 ml DCPD is mixed with 14 mg tricyclohexylphosphine and 5 µl phenylacetylene and then hardened (2 h / 80 ° C; 2 h / 120 ° C; 14 h / 140 ° C). A hard, brown polymer (T g = 95 ° C) is obtained.

    Beispiel 9Example 9

    Eine Lösung von 50 mg [(p-Cymol)RuCl2{tris(p-nonylphenyl)phosphit}] in 5 ml DCPD (94 %, Fa. Shell) wird mit 14 mg Tricyclohexylphosphin versetzt und anschließend ausgehärtet (2 h/80 °C; 2 h/ 120 °C; 10 h/140 °C). Dabei wird ein hartes Polymer (Tg = 128 °C) erhalten.A solution of 50 mg of [(p-cymene) RuCl 2 {tris (p-nonylphenyl) phosphite}] in 5 ml of DCPD (94%, Shell) is mixed with 14 mg of tricyclohexylphosphine and then cured (2 h / 80 ° C; 2 h / 120 ° C; 10 h / 140 ° C). A hard polymer (T g = 128 ° C) is obtained.

    Beispiel 10Example 10

    Eine Lösung von 150 mg [(p-Cymol)RuCl2{tris(p-nonylphenyl)phosphit)] in 10 ml DCPD (94 %, Fa. Shell) wird mit einer Lösung von 40 mg Tricyclohexylphosphin in 5 ml DCPD (94 %, Fa. Shell) versetzt und anschließend ausgehärtet (2 h/80 °C; 2 h/ 120 °C; 10 h/140 °C). Dabei wird ein hartes Polymer (Tg = 132 °C) erhalten.A solution of 150 mg [(p-cymene) RuCl 2 {tris (p-nonylphenyl) phosphite)] in 10 ml DCPD (94%, Shell) is mixed with a solution of 40 mg tricyclohexylphosphine in 5 ml DCPD (94% , Shell) and then hardened (2 h / 80 ° C; 2 h / 120 ° C; 10 h / 140 ° C). A hard polymer (T g = 132 ° C) is obtained.

    Beispiel 11Example 11

    Eine Lösung von 150 mg [(p-Cymol)RuCl2{tris(p-nonylphenyl)phosphit}] in 10 ml DCPD (94 %, Fa. Shell) wird mit einer Lösung von 35 mg Tris(isopropyl)phosphin in 5 ml DCPD (94 %, Fa. Shell) versetzt und anschließend ausgehärtet (2 h/80 °C; 2 h/120 °C; 10 h/140 °C). Dabei wird ein hartes Polymer (Tg = 130 °C) erhalten.A solution of 150 mg of [(p-cymene) RuCl 2 {tris (p-nonylphenyl) phosphite}] in 10 ml of DCPD (94%, Shell) is mixed with a solution of 35 mg of tris (isopropyl) phosphine in 5 ml DCPD (94%, Shell) added and then cured (2 h / 80 ° C; 2 h / 120 ° C; 10 h / 140 ° C). A hard polymer (T g = 130 ° C) is obtained.

    Claims (13)

    1. A catalyst system for the ring-opening metathesis polymerisation, which consists of at least two components (a) and (b), wherein
      (a) is a ruthenium compound of formula I or II RuX2(L1)m(L2)n(L3)o(L4)p ARuX2(L1)r(L2)s wherein L1, L2, L3 and L4 are each independently of the other C1-C18alkylcyanide, C6-C24aralkylcyanide, tertiary amine, tertiary phosphine which does not contain any secondary alkyl or cycloalkyl radicals bound to the phosphorus atom, or phosphite, X is halogen, A is arene, m, n, o and p are integers from 0 to 4, where 2 ≤ m + n + o + p ≤ 4, r and s are integers from 0 to 2, where 1 ≤ r + s ≤ 2, and
      (b) is a tertiary phosphine containing at least one secondary alkyl radical or cycloalkyl radical bound to the phosphorus atom.
    2. A catalyst system according to claim 1, wherein component (a) is a compound of formula I or II, wherein X is chloro.
    3. A catalyst system according to claim 1, wherein component (a) is a compound of formula II, wherein A is benzene, toluene, o-xylene, p-xylene, mesitylene, ethylbenzene, cumene, 1,3,5-triisopropylbenzene, p-cymene, durene, hexamethylbenzene, naphthalene, biphenyl or diphenylmethane.
    4. A catalyst system according to claim 1, wherein component (a) is a compound of formula I or II, wherein one or several ligands L1 to L4 are acetonitrile, propionitrile, n-butyronitrile, valeronitrile or capronitrile.
    5. A catalyst system according to claim 1, wherein component (a) is a compound of formula I or II, wherein one or several ligands L1 to L4 are triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tri(n-butyl)phosphine, tri(n-octyl)phosphine, trimethylphosphite, triisopropylphosphite, triphenylphosphite, tris(p-nonylphenyl)phosphite or a compound of formula III
      Figure 00170001
      wherein R is C1-C18alkyl, C5-C14aryl or C6-C24aralkyl.
    6. A catalyst system according to claim 1, wherein component (a) is a compound of formula II, wherein A is p-cymene, r is 2, and L1 is butyronitrile or capronitrile.
    7. A catalyst system according to claim 1, wherein component (a) is a compound of formula II, wherein A is p-cymene, r is 1, s is 0, and L1 is triphenylphosphite, tris(p-nonylphenyl)-phosphite or 2,4,8,10-tetrakis(1,1-dimethylethyl)-6-methoxydibenzo[d,f][1,3,2]dioxaphosphepine.
    8. A catalyst system according to claim 1, wherein component (b) is triisopropylphosphine or tricyclohexylphosphine.
    9. A curable two-component system, which consists of at least two components (c) and (d), wherein
      (c) is a mixture of 90.0-99.999 % by weight of a strained cycloolefin and of 0.001-10.0 % by weight of the component (a) according to claim 1, and
      (d) is a mixture of 90.0-99.999 % by weight of a strained cycloolefin and of 0.001-10.0 % by weight of the component (b) according to claim 1.
    10. A curable system according to claim 9, wherein the strained cycloolefin is a Diels-Alder adduct of cyclopentadiene.
    11. A process for the preparation of a metathesis polymer, which comprises heating a curable two-component system as claimed in claim 9 to a temperature of >40 °C.
    12. A process for the preparation of moulded articles, which comprises introducing a curable two-component system as claimed in claim 9 into a mould by the RIM process and curing it.
    13. Use of a curable two-component system as claimed in claim 9 as encapsulating material for electrical or electronic components.
    EP98810442A 1997-05-23 1998-05-14 Two-component catalyst for ring-opening metathesis polymerization Expired - Lifetime EP0885911B1 (en)

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